Synthesis and Reversible H2 Activation by Coordinatively Unsaturated Rhodium NHC Complexes

Autor:	Marius D. R. Lutz, Hongyu Zhong, Nils Trapp, Bill Morandi
Jazyk:	angličtina
Rok vydání:	2023
Předmět:	Inorganic Chemistry Reversible H2 activation Crystallography Coordinative unsaturation Hydrogenation N-Heterocyclic carbenes Rhodium Organic Chemistry Drug Discovery Physical and Theoretical Chemistry Biochemistry Catalysis
Zdroj:	Helvetica Chimica Acta, 106 (4)
ISSN:	0018-019X 1522-2675
Popis:	We report the synthesis of coordinatively unsaturated cationic rhodium complexes bearing the sterically encumbered electron-rich NHC ligand IPr*OMe. The COD (1,5-cyclooctadiene) complex [Rh(IPr*OMe)(COD)]BF4 adopts a tilted, pseudo-square planar coordination geometry, where bonding to the ipso-carbon of the NHC aryl substituent was observed in the solid state. Hydrogenation of this complex afforded a metastable dihydride complex [Rh(IPr*OMe)(H)2]BF4 with an unusual internal coordination to an arene of the ligand. In the absence of a hydrogen atmosphere, spontaneous reductive elimination of H2 afforded a rhodium complex [Rh(IPr*OMe)]BF4 with a single chelating ligand that stabilizes the highly unsaturated metal by two-fold π-face donation as suggested by NMR spectroscopy and computational studies. This unusual complex might serve as a versatile precatalyst for a variety of transformations. Helvetica Chimica Acta, 106 (4) ISSN:0018-019X ISSN:1522-2675
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_dedup___::b432a49777c6b7086b5b9436393a4ce4 https://hdl.handle.net/20.500.11850/604759 Zobrazit plný text záznamu Plný text